Phenyl-azo-hydroxynaphthoic acid amide pigments

ABSTRACT

AZO PIGMENTS OF THE FORMULA   R1-N=N-R2(-OH)-CO-NH-R3-X-NH-CO-NH-R4   IN WHICH R1 REPRESNETS AN AROMATIC RADICAL, R2 REPRESENTS A NAPHTHALENE RADICAL IN WHICH THE AZO, HYDROXY AND -CO-GROUPS ARE IN 1,2,3-POSITION, R3 REPRESENTS AN ARYLENE RADICAL, X REPRESENTS A DIRECT BOND OR A -COGROUP, AND R4 REPRESENTS A CARBAMIDE GROUP, AN ACYLAMINO GROUP OR AN ACYL OR CARBALKOXYALKYL RADICAL WHEN X REPRESENTS A DIRECT BOND, AND R4 REPRESENTS AN ALKYL OR ARYL RADICAL WHEN X REPRESENTS A -CO- GROUP. THEY ARE USEFUL FOR COLORING PLASTICS AND LACQUERS IN ORANGE TO RED SHADES.

United States Patent 3,660,373 PHENYL-AZO-HYDROXYNAPHTHOIC ACID AMIDE PIGMENTS Armand Roueche, Neu-Allschwil, Switzerland, assignor to Ciba Limited, Basel, Switzerland N0 Drawing. Filed Nov. 24, 1969, Ser. No. 879,615 filaims priority, application Switzerland, Dec. 12, 1968, 18,513/ 68 Int. Cl. C07!) 29/ 20; C07c 107/08 US. Cl. 260-203 6 Claims ABSTRACT OF THE DISCLOSURE Azo pigments of the formula This invention is based on the observation that valuable new azo pigments of the formula in which R represents an aromatic residue, R represents a naphthalene residue in which the azo, hydroxy and CO groups are in 1,2,3-position, R represents an arylene residue, X represents a direct bond or a CO- group and R represents a carbamide group that may be substituted by alkyl or aryl residues, an acylamino group, for example, a benzoylamino, formylamino, or alkanoylamino group, an acyl residue, for example, an alkanoyl, benzoyl or carbalkoxy group or a carbalkoxyalkyl group when X represents a direct bond, and R represents an alkyl or aryl group when X is a CO- group, may be obtained (a) by condensing a carboxylic acid halide of the formula R1-N=N13,2 0 01-1211 with an amine of the formula or (b) coupling a diazo or diazoamino compound of an aromatic amine with a coupling component of the formula Since the products of the invention are pigments, they must not contain groups imparting solubility in water, especially acid groups imparting solubility in Water, for example, sulphonic acid groups or carboxylic acid groups.

The carboxylic acids from which the acid halides required for process (a) of the invention are derived may be obtained by coupling a diazo compound of a carbocyclic or heterocyclic aromatic amine, especially an aminobenzene, with a 2,3-hydroxynaphthoic acid of the formula 3,663,373 Patented May 2, 1972 Z -COOH in which Z represents a hydrogen or a halogen atom or a nitro, cyano or alkoxy group,

Diazo components that are of special interest are those of the formula in which X represents a hydrogen or a halogen atom or an alkyl group and X and X each represents a hydrogen or a halogen atom or an alkyl, alkoxy, phenoxy, nitro, cyano, carboxylic acid ester, alkylsulphonyl, aralkylsulphonyl, trifluoromethyl, sulphonic acid amide or sulphonic acid ester group or a group of the formula CONH R, in which R represents a hydrogen atom, an alkyl group or a phenyl group that may be substituted, for example, by halogen atoms ar alkyl, trifluoromethyl, alkoxy, nitro, cyano, carbalkoxy or alkanoylamino groups.

The following aminobenzenes are given as examples of diazo components:

2-, 3- or 4-chl0roaniline, 3,4-dichloroaniline, 2,3-dich1oroani1ine, 2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline,

2-, 3- or 4-bromoaniline, 2,4-dibromoaniline, 2,5-dibromoaniline, Z-methyl-S-chloroaniline, 2-methyl-4-chloroaniline, 2-methyl-3-chloroaniline, 2-chloro-S-trifluoromethylaniline, 2-, 3 or 4-nitroaniline, 4-chloro-2-nitroaniline, 2-chloro-4-nitroaniline, 2-nitro-4-trifluoromethylaniline, 4-nitro-2-trifluoromethylaniline, 3,5di-(trifiuoromethyl)-ani1ine, 3-trifluoromethylaniline, 4-methyl-3-nitroaniline, 2,4-dimethyl-3nitroaniline, Z-methly-S-nitroaniline,

, 2-methyl-4-nitro aniline,

2- and 4-methoxyaniline,

3-chloro4-methoxyaniline,

Z-methoxy-S-nitroaniline,

2-methoxy-5chloroaniline, Z-methoxy-S-trifluoromethylaniline, 2-amino-4-trifluoromethy1-4'-chlorodiphenylether, 2-nitro-4-ethoxyaniline,

2-amino-4-chlorodiphenylether, 2-amino-2',4-dichlorodiphenylether, 2-amino-4,4-dichlorodiphenylether, 1-aminobenzene-Z-carboxylic acid rnethylester, 1 amino-Z-chlorobenzene-S-carboxylic acid rnethylester, 1amino2-chlorobenzene-S-carboxylic acid phenylester, 2-amino-5-nitr0benzoic acid rnethylester, 1amino-Z-methylbenzene-S-carboxylic acid rnethylester, 1-amino2-methylbenzene-5-carboxylic acid phenylester, 1amino-Z-chlorobenzene-5-carboxylic acid methylamide, 2-amino-4-trifluoromethyldiphenylether,

3 4-methyl-3-aminobenzoic acid amide, 4-chloro-3-aminobenzoic acid amide, 2,4-dichloro-S-aminobenzoic acid amide, 4-methoxy-3-aminobenzoic acid amide, 4-methyl-3-aminobenzoic acid-2'-chloro-5-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2',5'-dichloroanilide,

4-chloro-3-aminobenzoic acid-2-chloro-5-carbomethoxyanilide,

4-chloro-3-aminobenzoic acid- -chloroanilide,

4-chloro-3-aminobenzoic acid-2'-chloro-5-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-3'-trifiuoromethylanilide,

4-chloro-3-aminobenzoic acid-3,5'-bis-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2,4',S'-trichloroanilide,

2,4-dichloro-5-aminobenzoic acid-2,5'-dichloroanilide,

2,4-dichloro-S-aminobenzoic acid-2,4-dichloroanilide,

2,4-dichloro-S-aminobenzoic acid-3'-trifluoromethylanilide,

2,4-dichloro-S-aminobenzoic acid-3'-chloroanilide,

5-amino-4-methoxy-2-chlorobenzoic acid-3'-trifiuoromethylanilide,

4-methy1-3-aminobenzoic acid-2,5'-dichloroanilide,

4-methyl-3-aminobenzoic acid-3'-trifluoromethylanilide,

4-methoxy-3-aminobenzoic acid-3'-chloroanilide,

4-methoxy-3-aminobenzoic acid-2,5'-dichloroanilide,

4-methoxy-3-aminobenzoic acid-2',4',5'-trichloroanilide,

4-carbomethoxy-3-aminobenzoic acid anilide,

4-methoxy-3-aminobenzoic acid-3-trifiuoromethylanilide,

4-carbethoxy-3-aminobenzoic acid-2,5-dichloroanilide,

4-methoxy-3-amino'benzoic acid-3,5'-bis-trifluoromethylanilide,

4-methoxy-3-aminobenzoic acid-2'-chloro-5'-trifiuoromethylanilide,

4-methoxy-3-aminobenzoic acid-2,5'-dimethoxy-4'-chloroanilide,

4-methoxy-3-aminobenzoic acid-2',S-dimethyl-4-chloroanilide,

4-aminobenzoic acid-2',4'-dichlorophenylamide,

4-aminobenzoic acid-2-chloro-5-trifluoromethylphenylamide,

4-amino-3-methylbenzoic acid-3'-trifluoromethylphenylamide,

4-amino-3-methylbenzoic acid-4'-chlor0phenylamide,

4-amino-3-nitrobenzoic acid-2',5'-dichlorophenylamide,

4-amino-3-methylbenzoic acid methylester,

4-amino-3-methylbenzoic acid phenylester,

4-methoxy-3-aminobenzoic acid phenylester, and

4-methyl-3-aminobenzoic acid-para-chlorophenylester.

The azo dystuff carboxylic acids obtained are treated with substances which are capable of converting carboxylic acids into their acid halides, for example, their acid chlorides or bromides, such substances being, in particular, phosphorus halides, for example phosphorus pentabromide, phosphorus pentachloride or phosphorus trichloride, phosphorus oxyhalides and preferably thionyl chloride.

The treatment with the said acid halogenating agents is advantageously carried out in an inert organic solvent, for example dimethylformamide, a chlorobenzene, for example monochlorobenzene or a dichlorobenzene, toluene, xylene or nitrobenzene. If desired, dimethylformamide may be used in conjunction with the last five solvents specified. When preparing the carboxylic acid halides, it is generally advantageous first to dry the azo compounds which are prepared in an aqueous medium, or to free them from water by azeotropic distillation in an organic solvent. If desired, azeotropic drying may be carried out immediately prior to the treatment with the acid halogenating agents.

The azo dyestuif carboxylic acid chlorides so obtained are condensed with amines of the FQrmula 3, especially with those of the formulae H2NC -NHC ONHCOR 1 Y2 Elf;

H N-NHC o NHNHCOR HzN-NHC ONHCHzCOOAlk in which Y and Y each represents a hydrogen or a halogen atom or an alkyl or alkoxy group, R represents an amino or alkylamino group, a phenylamino group that may be substituted in the phenyl residue, for example, by halogen atoms or alkyl, alkoxy, trifluoromethyl, cyano, carbalkoxy or alkanoylamino groups, an alkyl or alkoxy group or a phenyl residue that may be substituted, R represents a hydrogen atom or an alkyl group or a phenyl residue that may be substituted, alk represents an alkyl group and R represents an alkyl group or a phenyl residue that may be substituted, for example, by halogen atoms or by alkyl, alkoxy, trifluoromethyl, cyano, carbalkoxy or alkanoylamino groups.

The following amines are given as examples:

4-aminophenyl- 1 -biuret,

4-amino-2,5-dimethylphenyl-l-biuret,

4-amino-2,5 -dichlorophenyl-1 -biuret,

4-amino-3-chloro-6-methoxyphenyll-biuret,

4-amino -2-methylphenyll biuret,

4-amino-2-chlorophenyl- 1 -biuret,

4-amino-2-methoxyphenyll-biuret,

4-amino-2,S-dimethoxyphenyll-biuret,

3-amino-4-chlorophenyl-1 biuret,

4-amino-2,5-diethoxyphenyll-biuret,

3 -amino-4-methylphenyL 1 -biuret,

N- 4-aminophenyl) -N-phenylbiuret,

N- 4-amino-2,S-dimethylphenyl) -N'-phenylbiuret,

N- (4-amino-2,S-dichlorophenyl) -N-phenylbiuret,

N- (4-aminophenyl) -N'-acetylbiuret,

N- (4-amino-2-methylphenyl) -N-phenylbiuret,

N- (4-aminophenyl) -N'- 3 ',4-dichlorophenyl -biu ret,

N-(4-aminophenyl -N- 4'-rnethoxyphenyl) -biuret,

N- (4-amino-2,S-dimethylphenyl) -N'- 4-chlorophenyl) biuret,

N- (4-amino-2,S-dichlorophenyl) -N'- 2'-methylphenyl biuret,

N- (4-aminophenyl) -N- 3 '-trifluoromethylphenyl) biuret,

N-( 3-amino-4-chlorophenyl) -N'-phenylbiuret,

1- 4-arnino) -phenylcarbamyl-2'b enzoylhydrazine,

1- (4-amino-2,5'-dimethyl -phenylcarbamyl-2- benzoylhydrazine,

1- (4'-amino2',5 '-dichloro -phenylcarbamyl) -2- (4"- chlorobenzoyl -hydrazine,

1-(4-amino) -phenylcarbamyl-2- (4"-methylbenzoyl hydrazine,

1- (4'-amino) -phenylcar-bamyl-2-formylhydrazine,

1- 4'-amino) -phenylcarbamyl-2- 2",4-dichlorolbenzoyl) -hydrazine,

1- (3 '-amino-4'-methyl) -phenylcarbamyl-2- (4"- b enzoyl) -hydrazine,

1- 4-amino-3 -chloro-6-methoxy) -phenylcarbamyl-2- benzoylhydrazine,

1- (4-amino -phenylcarbamyl-2-acetylhydrazine,

'y-(4-arninophenyl)-allophanic acid ethylester,

'y-(4-amino-2,5-dimethyl)-allophanic acid ethylester,

'y-(4-amino-2,5dichloro)-allophanic acid methylester,

N-(4-amino-3-chloro-6-methoxyphenyl) -N'-acetic acid methylester urea,

N-(4aminophenyl)-N'-acetic acid methylester urea,

N-(4-aminophenyl) -N'-acetic acid ethylester urea,

N-(4-amino-2,5-dimethylphenyl)-N'-acetic acid methylester urea,

N- (3-chloro-4-amino-6-methoxyphenyl) -N- benzoylurea,

N-(3-amino-4-methylphenyl)-N-benzoylurea,

N- (4-amino-2,5-dichlorophenyl)-N-benzoylurea,

N- (4-amino-2,5 -dimethylpheny1) -N-acetylurea,

N- (4-aminophenyl) -N- 2',5-dichlorobenzoyl) -urea,

N- (4-aminophenyl) -N'- (4 methoxybenzoy1)-urea,

N- (4-amino-2,5-dimethylphenyl) -N- (4-chlorobenzoyl) urea,

N-(3-amino-4-chlorophenyl)-N'- (4-chlorobenzoyl) -urea,

N- (4-aminobenzoy1)-N-(4-chlorophenyl)-urea,

N-(4-aminobenzoyl) -N- (2,4-dichlorophenyl) -urea,

N- 4-amino-3-methylbenzoyl) -N- (4'-chlorophenyl) urea and N-(4-aminobenzoyl)N-phenylurea.

Condensation between the carboxylic acid halides of the kind defined above and the amines is advantageously carried out in an anhydrous medium. Under these conditions it generally proceeds surprisingly easily, even at temperatures within the boiling range of the common organic solvents, for example, toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like. To accelerate the reaction, it is generally advantageous to use an agent capable of binding acid, for example, anhydrous sodium acetate or pyridine. Some of the products obtained are crystalline and some are amorphous and they are generally obtained in a very good yield and in a pure state. It is expedient first to isolate the acid chlorides obtained from the carboxylic acids. In some cases however, isolation of the acid chlorides may be omitted without harm and condensation may be carried out immediately after preparation of the carboxylic acid chlorides.

In process (b) of the invention, the new pigments may be obtained by coupling a diazotized aromatic amine, preferably a diazotized aminobenzene, especially one of Formula 6, with a coupling component of Formula 4.

The coupling components mentioned may be obtained by condensing a 2,3-hydroxynaphthoic acid chloride with an amine of the Formula 3, especially an amine corresponding to one of the Formulae 7 to 10.

Coupling may be eifected by gradual addition of an aqueous alkaline solution of the coupling component to an acidic solution of the diazonium salt. Coupling is advantageously carried out at a pH value of 4 to 6. The pH value is advantageously adjusted by the addition of a buffer. Suitable buffers are, for example, the salts, especially the alkali metal salts, of formic acid, phosphoric acid or especially acetic acid. The alkali solution of the coupling component advantageously contains a wetting agent, a dispersing agent or an emulsifying agent, for example, an aralkyl sulphonate, for example, dodecylbenzene sulphonate or the sodium salt of l,l'-naphthylmethane sulphonic acid, polycondensation products of alkylene oxides, for example, the product obtained by reacting ethylene oxide With para-tertiary-octylphenol, and also the alkylesters of sulphoricinoleates, for example, nbutyl-sulphoricinoleate. The dispersion of the coupling component may also advantageously contain protective colloids, for example methylcellulose or small amounts of inert organic solvents which are sparingly soluble or insoluble in water, for example, aromatic hydrocarbons, which may be halogenated or nitrated, for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene, as well as aliphatic halogenated hydrocarbons, for example, carbon tetrachloride or trichloroethylene; also suitable are organic solvents miscible with water, for example, acetone, methylethyl-ketone, methanol, ethanol or isopropanol.

Coupling may also be carried out with advantage by continuously combining an acidic solution of the diazo nium salt with an alkaline solution of the coupling component in a mixing nozzle whereby coupling takes place instantaneously. The pigment dispersion formed is removed continuously from the mixing nozzle and the pigment is isolated by filtration.

The aryldiazoamino compounds to be used in process (b) of the invention may be obtained by known methods by coupling an aryldiazonium salt with a primary or preferably secondary amine. A very wide variety of amines are suitable for this purpose, for example, aliphatic amines, for example, methylamine, ethylamine, ethanolamine, propylamine, butylamine, hexylamine and especially dimethylamine, diethylamine, diethanolamine, methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic acid, butylaminoacetic acid, aminoethane sulphonic acid, methylaminoethane sulphonic acid, guanylethane sulphonic acid and ,B-aminoethyl sulphonic acid; alicyclic amines, for example, cyclohexylamine, N- methylcyclohexylamine and dicyclohexylamine; aromatic amines, for example, 4-aminobenzoic acid, sulphanilic acid, 4-sulpho-2-aminobenzoic acid, (4-sulphophenyl)- guanidine, N-4-methylaminobenzoic acid, 4-ethylaminobenzoic acid, l-aminonaphthalene-4-sulphonic acid and l-aminonaphthalene 2,4 disulphonic acid; heterocyclic amines, for example, piperidine, morpholine, pyrrolidine, dihydroindole and also sodium cyanamide or dicyanodiamide.

Generally, the diazoamino compounds obtained are sparingly soluble in cold water and, if necessary, may be separated from the reaction medium in a crystalline form after salting out. In many cases, the moist press cake may be used as it is in further reactions. In some cases, it may be advantageous to dehydrate the diazoamino compounds by vacuum drying prior to the reaction.

Coupling of the diazoamino compound with the coupling component may be carried out in an organic solvent, for example, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, pyridine, ethylene glycol, ethylene glycol monoethyl ether or ethylene glycol monomethyl ether, dimethylformamide, formic acid or acetic acid. When using a solvent which is miscible with water, it is not necessary to use the diazoamino compound in an anhydrous form. For example, the water-moist filter cake may be used.

Coupling may be advantageously carried out with the application of heat, preferably at a temperature Within the range of from 8-0 to C. in an acid medium, and it generally proceeds very quickly and is complete. When a neutral solvent is used it is advantageous to add an acid, for example, hydrochloric acid, sulphuric acid, formic acid or acetic acid. By virtue of their insolubility, the pigments obtained may be isolated from the reaction mixture by filtration. Thus, an after-treatment with an organic solvent, to which pigments that have been obtained by coupling in an aqueous medium have to be subjected, is not necessary in most cases.

The new products are valuable pigments that may be used for a very wide variety of purposes. For example, they may be used in a state of fine division for the spincolouration of filament and staple-fibre viscose, cellulose ethers, cellulose esters, polyamides, polyurethanes and polyesters, and also in the production of coloured lacquers and lake-formers, solutions or products made from cellulose acetate, nitrocellulose, natural or synthetic resins, for example, polymerization resins or condensation resins, for example, aminoplasts, alkyd resins and phenoplasts, and also polyolefines, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, rubber casein, silicones and silicone resins. They may also be used with advantage in the manufacture of coloured pencils, printing pastes, cosmetic preparations and laminated sheet material.

The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

EXAMPLE 1 47.5 parts of the dyestuff obtained by diazotizing 2,4,5- trichloroaniline with glacial acetic acid, hydrochloric acid and sodium nitrite, and coupling with 2,3-hydroxynaphthoic acid are heated for two hours at 135 to 145 C., with 650 parts of ortho-dichlorobenzene, 20 parts of thionyl chloride and 2 parts of dimethylformamide while stirring; dissolution is complete. After cooling the reaction mixture, the uniformly crystalline monocarboxylic acid chloride of the dyestuff is isolated by filtration and washed successively with 400 parts of benzene and 200 parts of petroleum ether. After drying in vacuo at 50 to 60 C., 39 parts of the dyestulf acid chloride are obtained in the form of a red crystalline powder.

5.0 parts of the acid chloride so obtained are stirred in 450 parts of ortho-dichlorobenzene and the batch is heated to 100 C. A warm solution of 2.4 parts of 4- aminophenyl-l-biuret in 20 parts of dimethylformamide is added and the batch is heated for 12 hours at 140 to 145 C. The finely crystalline, sparingly soluble pigment is then isolated by filtration while hot, washed with hot orthodichlorobenzene until the filtrate runs clear, and it is then Washed successively with cold methanol and hot water. After drying in vacuo at 80 to 85 C., 4.4 parts of a soft powder are obtained which is virtually insoluble in the common solvents and which colours polyvinyl chloride film and also lacquers a brown shade possessing excellent fastness to light, migration and overstripe bleeding.

The pigment corresponds to the formula ONHC -NHC ONHC ONHz EXAMPLE 2 36.5 parts of the dyestuff obtained by coupling diazotized 2,5-dichloroaniline with 2,3-hydroxynapl1thoic acid I are heated for 2 hours at 135 to 145 C. while stirring, with 390 parts of ortho-dichlorobenzene, 165 parts of thionyl chloride and 2 parts of dimethylformamide; dissolution is complete. After cooling the reaction mixture, the uniformly crystalline azo dyestufi' monocarboxylic acid chloride is isolated by filtration and washed successively with 400 parts of benzene and 200 parts of petroleum ether. After drying in vacuo at 50 C., 29.5 parts of a red crystalline powder are obtained.

5.7 parts of the azo dyestufi carboxylic acid chloride so obtained are stirred in 400 parts of dichlorobenzene and the batch is heated to 80 to 90 C. A warm suspension of 5.0 parts of N-(4-amino-2,5-dichlorophenyl)-N'-benzoylurea in 40 parts of dimethylformamide is added and the batch is heated for 12 hours at 140 to 145 C. The finely crystalline, sparingly soluble pigment that precipitates is then isolated by filtration while hot, Washed with hot ortho-dichlorobenzene until the filtrate runs colourless, and it is then washed successively with cold methanol and hot Water. After drying in vacuo at 80 C., 6.5 parts of a soft-grained powder are obtained which is virtually insoluble in the common solvents and which colours polyvinyl chloride film and also lacquers a red shade possessing excellent fastness to light, migration and overstripe bleeding.

The pigment corresponds to the formula 84 parts of the dyestuif obtained by diazotizing 5-trifluoromethyl-Z-chloro-l-aminobenzene with aqueous hydrochloric acid and sodium nitrite, and coupling with 2,3- hydroxynaphthoic acid are heated for one hour at 75 to C. with 1500 parts of benzene, 35 parts of thionyl chloride and 2 parts of dimethylformamide while stirring. After cooling the reaction mixture, the uniformly crystalline monocarboxylic acid chloride of the dyestutf is isolated by filtration, washed with cold benzene and then dried in vacuo at 50 to 60 C.

2.5 parts of the acid chloride so obtained are stirred in 230 parts of ortho-dichlorobenzene and the batch is heated to C. A warm solution of 1.9 parts of 1-(4'- amino 2',5' dimethylphenylcarbamyl) 2 benzoylhydrazine in 10 parts of dimethylformamide is added and the batch is heated for 12 hours at to C. The finely crystalline, sparingly soluble pigment is then isolated by filtration while hot, washed successively with hot ortho-dichlorobenzene, cold methanol and hot water and then dried in vacuo at 70 to 80 C.

The product so obtained of the formula OH I C ONE-OHNC ONHNHC 0O EXAMPLE 4 27.2 parts of the dyestulf obtained by diazotizing 4- methoxy-3-aminobenzoic acid-(2'-chloro-5-trifluoromethyl)-phenylamide in glacial acetic acid and hydrochloric acid with sodium nitrite and coupling with 2,3-hydroxynaphthoic acid are heated for 10 hours at 55 to 60 C. with 650 parts of chlorobenzene, 11.5 parts of thionyl chloride and 3.5 parts of dimethylformamide while stirring. After cooling the reaction mixture, the uniformly crystalline monocarboxylic acid chloride of the dyestulf is isolated by filtration, washed with cold benzene and dried in vacuo at 50 C.

2.25 parts of the acid chloride so obtained are stirred phenyl)-allophanic acid ethyl ester in parts of dimethylin 150 parts of ortho-dichlorobenzene and the batch is formamide is added at 80 C. The batch is heated to 140 heated to 70 C. A warm solution of 1.2 parts of N-(4- C. and stirred for 8 hours at 140 to 145 C. The batch aminobenzoyl)-N'-(4-chlorophenyl)-urea in 7 parts of is then vacuum-filtered and the filter residue is Washed dimethylformamide is added and the batch is heated for 5 successively with hot ortho-dichlorobenzene, cold meth- 12 hours at 140 to 145 C. The crystalline, sparingly solanol and hot water and dried in vacuo at 70 to 80 C.

uble pigment is then isolated by filtration while hot, The product so obtained of the formula washed successively with hot ortho-dichlorobenzene, cold N02 methanol and hot water, and dried in vacuo at 70 to 80 C. The product so obtained of the formula OCH I I ll ooNH-- NE-O-rrnc ONHC o 0 0211.

1 ONHOC ONHO C is a finely crystalline claret pigment that is sparingly soluble to insoluble in the common solvents. is a bluish red pigment that is sparingly soluble to insol- It colours P mammals example, P W Y uble in the common solvents and that colours polyvinyl chloride, and also l f brilliant fllaret P- chloride film and also lacquers a bluish red shade possess- Very good fame to mlgratlon, ovefstflpe lbleedmg and ing excellent fastness to light, migration and overstripe lightb1eeding The following table lists components for making further monoazo pigments. The pigments may be obtained EXAMPLE 5 by coupling 1 mol of a diazo compound of an amine 17.3 parts of diazotized 2-nitro-4-chloroaniline are coulisted in column I with 1 mol of 2,3-hydroxynaphthoic pled in the usual manner with 18.8 parts of 2,3-hydroxyacid as shown in column II in the manner described in naphthoic acid. The azo dyestulf so obtained is dried and the first paragraph of the above example, the monoazo then converted into the azo dyestufi carboxylic acid halide dyestutf carboxylic acid so obtained is converted into the with thionyl chloride in ortho-dichlorobenzene. acid chloride, and the latter is condensed with 1 mol of 1.2 parts of the monoazo dyestuff carboxylic acid chloan amine as listed in column H1. The shades which the ride so obtained are stirred in 130 parts of ortho-dichloropigments produce in polyvinyl chloride film are indicated benzene, and a hot solution of 0.75 part of 'y(4-am1nO- in column IV.

I II III IV 1 2,4,5-trieh1oroanlline 2,3-hydroxynaphthoic acid 4-a1m'no-2,5-dimethylphenyl-1-biuret Brown 2 2,5-rlir-hlnrnaniline d0 d0 a e 3 do- 110.- 4am.inopheny1-1-biuret Red, 4...-.- 2,5-d1chloroaml1ne fl-bromo- -hydroxynaphthoic acid- 4aminophenyla-biuret Red. 5 do do- 4-amino-2,5-di.rnethylpheny iurct Red. 6 2-chloroIi-tr1fluor0methy1am1ine 2,3-hydroxynaphthoic acid 4-aminophenyl-1-biuret- Orange 7 2-nitro-4chloroani1ine d Br wn 8 z-nitro-lrtrifiuoromethylanitina Do 9 3-amino-4-chlorobenzoic acid-2'-chloro-5- Reddish trifluoromethylanillde. orange, 10 3-amino-4-chlorobenzoie acld-3trifluoro- Red.

methylanilide. 11 2-nitro-4-trifiuoromethyla do N-(4aminophenyl)-N-pheny1biuret Brown. 12 2,5-dichlor do do- Orange. 13 do. do- N-(4-amiuo-2,5-dimethylphenyl)-N- Red.

phenylbiuret. 14 3-amino-4-chlorobenzoic acid-2-chloro-5- do N-(l-aminophenyl)-N-phenylbiuret Red.

trifluoromethylanilide. 15 2-methoxy-4-nitroanillne- .-do l-g l -grmirilo)-phenylcarbamyl-2-benzoyl- Claret.

y az ne. 16 2-chloro-5-trifluoromethylani1inedodo- Orange. 17 2,5-dichlor do do- Red. 18 dodo- 1-(4'-amino-2,5-dimethyl) -pheny1- Red.

carbamyLZ-benzoyl hydrazine. 19 2,4,5-trichloroaniline do o- Red. 20 3-amino-4-chlorobenzoic acid-2'-methyl-3- d0 1-(4-aminophenyloarbamyl)2-benzoyl- Reddish chloroanilide. hydrazine. orange. 21 3-amino-4-ch1orobenzoic acid-3-ca.rbodo .do Do.

methoxyanilide. 22. 3-amino-4-methylbenzoic acid-3-trifluorodo do Red.

methylanilide. 23 3-amino-4,6-dichlorobenzoic acid-2,4- .-do do Red.

dichloro 'lide. 24..." 2,5-dichloroaniline 6-methoxy-2,3-hydroxynaphthoic acid..." 1-(4-amino-2,5-dimethy1phenyl- Bluish carbamyl)-2-benzoylhydrazine. red. 25 3-amino-4,6-dichlor0benzoic acid-2,4- 2,3-hydroxynaphthoic acid 'y-(4-aminophenyD-al1ophanic acid Brown.

dichloroanilide. ethylester. 26..- 8-amino-4-methoxybenzoic acid-8 do N-(4-amino3chloro-fi-methoxyphenyl)- Bluish trifiuoromethylanilide. N -acetic acid methylester urea. red. 27 3-amino-4-methylbenzoic acid-3- do .do Red.

tn'fluoromethylanilide. 28.. 2,5-dichloroaniline .do N-(3-o1110l0-4-amin0-6-methoxyphenyl)- Brown.

N-benzoylurea. 29 2-nitro-4-trifiuoromethylaniline N-(3-amino-4-methylphenyl)-N- Red.

benzoylurea. 30. Z-chloro-5-trifluoromethylani1ine N-(4-aminophenyl)-N-benzoylurea Orange. 31 2-methoxy-4-nitroaniline do Bluigh re 32 3-amino4-methylbenzoic acid-3-tri- N-(eaminophenyl)-N-4-chloro- Red.

fluoromethylauilide. benzoylurea. 33 fi-aminol-methoxybenzoic acid-3-tri .do N-(4-aminophenyl)-N-benzoy1urea Bluish fluoromethylauilide. red. 34 3-amino-4-chlorobenzoic acid-3-trido do Red.

fluoromethylanilide. 35--.. 2-nitro-4-trifluoromethy1aniline -do N-(4-aminobenzoyl)-N-(4-eh1oro- Orange.

phenyl) -urea.

TABLE-Cntinucd I II III IV 36 3-aniino-4-chlorobenzoic aeid-Btri- 2,3-hydroxynapthalcno acid N-(4-amin0phcuyl)-N-acctylurea Rcd.

iluoromethylanilidc. 37.- 2,5-dic1110roaniline do. N-(4-aminopheuyl)-N-methylbiurct Red. 38"... 3-amino-4-chlorobenzoic aeid-2-chloro-5 do 1-(4-am.inophenyl)-carbamyl-2-formyl- Orange.

trifluoromethylanilidc. hydrazine. 30 do .do 1-(4-aminophenyl)-carbamyl-2-acctyl- Red.

' hydrazine. 40... 2,5-dicl1loroaniline 6-nitr0-2,3hydr0xynaphthoic acid 4-amino-2,5-dimcthylphenyl-l-biuret Red. 41 do 2,3-hydroxynaphth0ic acid N-(4-aminophenyl)-N-a-naphthylbiurct Rcddish orange. 4.. do do N-(4-aminophenyl)-N-benzoylurea. Red. 43 .do 6-brorn0-2,3-hydroxynaphthoic acid. N-(4-amino-2,5-dimcthylphenyl)-N- Brown benzoylurea. 44 do 6-methoxy-2,3-hydroxynaphthoic acid w do 45." do 2,3-hydroxynaphtholc acid do 4G .do 6-nitr0-2,3-hydr0xynpahthoic acid N-(4-amino-2,S-diehloroplieny zoylurea. 47 do do N-(4-aminophcnyl)-N-bcnzoylurca Brown. 48 do 6bromo-2,3-liydroxynaphtlroic acid 1-(4-amino-2,5-dimethylplicnyl)car- Rcd.

barnyl-2-benzoylhydrazine. lfL do 2,3-liydroxynaphthoic acid 1(3-amin0-4-methylphenyl)-carbamyl- Orange.

2-(2,5"-dichloro)-benzoylhydrazinc. 50 do d0 1-(4-aminophenyl)-carbamyl-LZ-(W-mcthyl- Red.

benzoyD-hydrazine. 51 .d0 do 1-(4-amin02'-methoxy-(Y-chloro)-plicnyl- Red.

carbamyl-2-(4-rneth0xybenzoyl)-hydra- Zinc. 52 do 6-nitro-2,3-hydroxynaphthoic acid 1-(4-amin0phenyl)earbamyl-2-(3",4- Bluish dlchlorobenzoyl)hydrazine. red. 53 do 6-bron1o-2,3-hydroxynaphtl1ioc acid 1-(4-aminophenyl)-carbamy1-2-(2,4- Red.

dicl1lorobcnz0yl)-hydrazine. -1-.. 2-nitro-4-trifluoromcthylanillne 2,3-hydroxynaphthoic acid 1-(3-amin0 l-methylphenyl)-carbamyl2 Orange.

(2 ,5 -dichlor0benz0y1)-hydrazine. 55 "do do 1-(3-aminophenyl)-earbamyl-2-bcnzoyl- Do.

benzoylhydrazine. 56 2-chl0r0-5triilu0r0mcthylaniline do 1-(-t-aminophcnyl)-carbamyl-2-(4- Red.

methylbenzoyl)-hydrazine. 571.... 2-benzylsulphone-fi-trifiuoromethyldo 1-(4-aminoplienyl)-carbamyl-2-benzoyl- Orange.

aniline. hydrazine. 5S .do do 4-amino-2,6-dimethylphcnyl-l-biuret D0. 59. 3-arnino4-methylbenzoic acid phenylester do 1-(4-aminophcnyl)-carbamyl-2-(4- Scarlet.

methylbenzoyl)-hydrazlne. 60 3-amino4-mcthylbcnzoie acid-4-chlorod0 do Do.

phenyl ester. 61 do do 1-(4-amino2,5-dimethylphenyl)-car- Do.

bamyl-2-bcnzoylhydrazinc. 62. 2-ethylsulionylfi-trifiuoromethylaniline ..d0 1-(4-aminophcnyl)-2-(4-methylbenzoyl)- Orange.

hydrazine.

EXAMPLE 6 3.25 parts of 2,5-dichloro-l-aminobenzene are diazotized in the usual manner with aqueous hydrochloric acid, ice and sodium nitrite.

Separately from this, 7.85 parts of 4-(2"-hydroXy-3- naphthoylamino)-2,5-dimethylphenyl 1 biuret are dissolved cold in a mixture of 150 parts of ethanol, 50 parts of water and 5.0 parts of 30%( sodium hydroxide solution. 1 part of the condensation product obtained from 8 mols of ethylene oxide and 1 mol of para-tertiary-octylphenol is added to the solution, and the naphthol is then precipitated with acetic acid while vigorously stirring. Coupling is effected by the addition of the diazo solution described in the preceding paragraph at a pH value of 5.5 to 6.5 and a temperature of to C. The batch is stirred for 1 hour at the same temperature to complete the coupling and then for 1 hour at 70 to 80 C. The pigment suspension so formed is rendered acid to Congo paper by the addition of hydrochloric acid and then filtered. The product is washed with hot water until chlorine ions are no longer detectable in the filtrate and then dried in vacuo at 80 to 90 C. An orange pigment of the formula is obtained in a good yield.

The properties of the pigment can be improved by an after-treatment in an organic solvent, for example, nitrobenzene. It is sparingly soluble to insoluble in the common solvents and colours polyvinyl chloride film and also lacquers a reddish orange shade possessing good fastness to migration, overstripe bleeding and light.

EXAMPLE 7 1.5 parts of the diazoamino compound of the formula prepared by coupling diazotized 3-amino-4-methoxybenzoic acid-3'-trifiuoromethylanilide with morpholine in an alkaline medium, and 1.4 parts of N-[3-chloro-6-methoxy- 4-(2"-hydroxy 3" naphthoylamino)-phenyl]-N'-acetic acid methylcster urea are suspended in 130 parts of orthodichlorobenzene, the suspension is heated to to C., and 8 parts of glacial acetic acid are added. The batch is then stirred for 1 hour at to C., during which cleavage of the diazoamino compound and coupling to form the pigment is completed. The red pigment is isolated by filtration while hot, washed successively with hot ortho-dichlorobenzene, cold methanol and hot water and then dried in vacuo at 80 C. 1.8 parts of a bluish red monoazo pigment of the formula OCH;

N=N-Q or, I -Q OH 01 -c ONH- NHC oNnonzoooom are obtained in a soft form. It is sparingly soluble to insoluble in the common solvents and colours polyvinyl chloride film and also lacquers a bluish red shade possessing good fastness to migration, overstripe bleeding and light.

EXAMPLE 8 A mixture is prepared from 65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the pigment obtained in the manner described in Example 1 and then worked to and fro for 7 minutes on a two-roller mill at 140 C. A pure, brown film is obtained possessing very good fastness to light and migration.

1 claim:

1. An azo pigment of the formula in which X is hydrogen, chloro, bromo or lower alkyl, X and X each is hydrogen, chloro, bromo, lower alkyl, lower alkoxy, phenoxy, nitro, cyano, lower carbalkoxy, carbophenoxy, lower alkylsulfonyl, trifluoromethyl or a group of the formula CONH,R, in which R is hydrogen, lower alkyl, phenyl or phenyl substituted by chlorine, lower, alkyl, lower alkoxy, trifluoro'methyl or lower carbalkoxy, Z is hydrogen, bromine, lower alkoxy, nitro or cyano, Y and Y each is hydrogen, halogen, lower alkyl or lower alkoxy, X is a direct bond when R, is COR NHCOR or OH OO lower alkyl, or X is CO- when R, is lower alkyl, phenyl or phenyl substituted by chlorine, lower alkyl, lower alkoxy, trifiuoromethyl or cyano; R is amino, lower alkyl amino, lower alkyl, lower alkoxy, phenyl, naphthylamino, anilino or anilino substituted by chlorine, lower alkyl, lower alkoxy or trifluoromethyl; and R is hydrogen, lower alkyl, phenyl or phenyl substituted by chlorine, lower alkyl or lower alkoxy.

l4 2. The compound as claimed in claim 1 of the formula N=N 5 I OH 1 Cl CONHONHCONHC 0-6 10 $1 3. The compound as claimed in claim 1 of the formula SOBCH2CQH OH F;

-o o NHONHCONHC ONE, 4. The compound as claimed in claim 1 of the formula OH (3H3 CONH NHCONHNHCO-Q 5. The compound as claimed in claim 1 of the formula a -Q 40 OH or;

CONHC NHCONHCHZCOOCH3 6. The compound as claimed in claim 1 of the formula 01 CONH- NHCONHCONH References Cited UNITED STATES PATENTS 3,472,834 10/1969 Ronco et al. 260204 X JOSEPH REBOLD, Primary Examiner C. F. WARREN, Assistant Examiner US. Cl. X.R.

260-l40, 204, 553, A, B, E, 554, 31.8 PQ, 41.5 R 

